CN116328663A - Slurry bed reactor, poor-quality oil slurry bed hydrocracking system and method - Google Patents
Slurry bed reactor, poor-quality oil slurry bed hydrocracking system and method Download PDFInfo
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- CN116328663A CN116328663A CN202111546056.3A CN202111546056A CN116328663A CN 116328663 A CN116328663 A CN 116328663A CN 202111546056 A CN202111546056 A CN 202111546056A CN 116328663 A CN116328663 A CN 116328663A
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 222
- 239000003921 oil Substances 0.000 claims abstract description 140
- 239000000463 material Substances 0.000 claims abstract description 35
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- 238000007670 refining Methods 0.000 claims description 73
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- 239000002184 metal Substances 0.000 claims description 12
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- 239000002199 base oil Substances 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
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- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 3
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a slurry bed reactor, a poor-quality oil slurry bed hydrocracking system and a poor-quality oil slurry bed hydrocracking method. The outlet of the reactor is arranged at the top of the shell; the reactor inlet is arranged at the bottom of the shell; the built-in empty barrel is arranged in the shell, and spiral fins are arranged between the built-in empty barrel and the shell. According to the invention, the empty barrel with the spiral channel is arranged in the slurry bed reactor, so that materials in the slurry bed reactor flow in a spiral rising mode, the mass transfer is enhanced, and the material flow mode in the slurry bed reactor is optimized; the system and the method for hydrocracking the inferior heavy oil slurry bed can control the coking of the inferior heavy oil slurry bed hydrocracking reaction, realize the safe and stable operation of the inferior heavy oil slurry bed hydrocracking device, and effectively prolong the operation period of the device.
Description
Technical Field
The invention belongs to the field of oil refining, in particular to the field of poor quality and heavy oil deep processing in heavy oil lightening, relates to heavy oil slurry bed hydrogenation equipment and a process, and particularly relates to a slurry bed reactor, a poor quality oil slurry bed hydrocracking system and a method.
Background
Aiming at inferior oil, processes such as heavy oil catalytic cracking (raw material requirement: carbon residue value is lower than 8%, total metal content is not more than 20 mug/g) and heavy oil fixed bed hydrotreating (raw material requirement: carbon residue value is lower than 15%, total metal content is not more than 200 mug/g) are adopted, and the catalyst surface is very fast due to coking and metal deposition; the delayed coking process has high coke yield and poor coke quality (high sulfur content and ash content of the coke), and shot coke can be generated in a coke tower to influence the safe operation of a coking device; the boiling bed hydrogenation technology can be used for processing inferior heavy oil, but the process flow and equipment are complex, and the light oil yield is lower. Compared with the technology, the heavy oil slurry bed hydrocracking technology can process inferior raw materials, has better product quality and light oil yield, and is a currently more suitable technology.
Currently, the mainstream heavy oil slurry bed hydrocracking process includes several types of: the EST process of Italy ENI company, the HDHPLUS-SHP process developed by combining Venezuela PDVSA with Axens in France, the VRSH process of Chevron company, the VCC process of KBR and BP, the Uniflex process of UOP company have advantages and characteristics, but have great differences in the operation conditions, the types of catalysts, the technical scheme and the like.
EST technology uses an oil-soluble residuum slurry bed hydrocracking catalyst, and is converted into nano-scale thin-layer MoS without carrier in slurry bed reactor 2 And adopts complex technology for controlling the process in the reactor, and has the main characteristics that: (1) the unconverted oil is recycled for multiple times, the total conversion rate of the raw oil is high, and no fuel oil or coke products are generated; (2) the product quality is better, and the gasoline and diesel oil meet the European IV standard; (3) the metal in the raw oil is basically removed; (4) the consumption of the catalyst with higher cost is less.
The HDHPLUS-SHP process is provided with two slurry bed reactors with complex internal components to operate in series, a solid particle catalyst is used, a certain amount of auxiliary agent is needed to be added, the catalyst system has insufficient dispersibility in raw oil, and a harsher reaction process condition is adopted, so that about 10% of unconverted tail oil is needed to be thrown outwards, and the device economy is insufficient.
The VCC technology adopts a nonmetallic slurry-state bed hydrocracking catalyst, and a plurality of reactors are operated in series, so that the influence of back mixing of reaction materials is reduced. The operating pressure is 18-20 MPa, and the single pass conversion rate of the residual oil can reach 95% by increasing the reaction severity. In the thermal separator, light components are separated from unconverted tail oil, the unconverted tail oil is completely discharged from the bottom of the thermal separator, no circulating treatment is carried out, the purposes of controlling coke formation and maintaining stable operation of the device are achieved through the discharged tail oil, and the economical efficiency of the device is poor.
Chinese patent CN201510190769.9 discloses a two-stage heavy oil slurry bed hydrogenation apparatus and method, which comprises a two-stage slurry bed hydrocracking system, each stage is provided with a reactor comprising a riser and a downcomer and a separator, and apparatus for enhancing the flow of reaction materials such as a distributor, a demister, an expansion section, etc. are arranged in the reactor.
The disadvantages of this technique or the shortcomings with respect to the present invention: the reactor of the method contains more internal components, the reactor structure is complex, if coke formation and aggregation in the reactor are difficult to clean, and meanwhile, the reactor with the complex structure also brings difficulty to the stable operation of the device.
Chinese patent CN201410367441.5 discloses a two-stage hydrogenation refining method for inferior oil. The method adopts a process flow of connecting two fixed bed reactors in series, the inferior heavy oil raw material is subjected to hydrocracking treatment through a first-stage slurry bed reactor, light and heavy components are separated through a high-temperature separator, then heavy components enter a second-stage slurry bed reactor for hydrocracking treatment, the reaction product is separated into light and heavy components through the high-temperature separator, the heavy components are separated through reduced pressure distillation to remove solid impurities, and the reduced pressure distillate and the light components of the two-stage slurry bed enter the fixed bed reactor for refining treatment to obtain high-quality light distillate.
The disadvantages of this technique or the shortcomings with respect to the present invention: the method is characterized in that with the extension of the running time of the device, solid particle impurities of the reaction coke and the catalyst are easy to accumulate in a high-temperature separator and a vacuum fractionating tower to block equipment, and meanwhile, due to the limited capability of separating the solid impurities of the two equipment, subsequent process pipelines and equipment are blocked, especially if the blockage occurs in a bed layer of a fixed bed reactor, the pressure drop of the fixed bed reactor is increased, and the running period of the whole device is influenced. In addition, the method uses the waste agent of the iron-based desulfurizing agent as a main agent, and a slurry bed catalyst system of bituminous coal, sulfur or organic sulfide is added, so that the dispersion degree of the catalyst in raw oil is poor, and the activity of inhibiting the coking reaction and hydrogenation is insufficient.
Chinese patent CN201410276723.4 discloses a residuum slurry bed hydrocracking method and apparatus. The method adopts a process flow of a slurry bed and a fixed bed, and is characterized in that inferior heavy oil raw materials are treated by a slurry bed reactor, light and heavy components are separated by fractionation equipment and then enter the fixed bed reactor for hydrofining or hydrocracking treatment, so that high-quality light distillate oil is obtained.
The disadvantages of this technique or the shortcomings with respect to the present invention: the method does not provide special hydrogen mixing equipment, and uses a pipeline hydrogen injection mode to mix hydrogen, so that the hydrogen mixing effect is poor. The slurry bed catalyst is solid particles prepared by mixing, spraying and granulating iron powder and ammonium molybdate, and the dispersion effect of the slurry bed catalyst in the poor raw materials is poor, so that the activity of the slurry bed catalyst is limited. The mixture of the raw coke, asphaltene, heavy metal and catalyst is discharged from the bottom of a high-temperature and high-pressure separator, the solid discharge process of the high-temperature and high-pressure separator has great risks and potential safety hazards, and a proprietary technology is required, and the method is not explicitly described. In addition, the method is not provided with special solid removing equipment, and as the running time of the whole system is prolonged, residual catalyst solid particles, reaction coke and other impurities can block the bed layer of the fixed bed reactor to cause the rise of pressure drop of the reactor, thereby influencing the stable running of the device.
Chinese patent CN201210241249.2 discloses a high-efficiency inferior heavy oil and residual oil hydrotreating process, which adopts a process flow that slurry bed reactors are connected in series with a plurality of fixed bed reactors with different functions, firstly, inferior heavy oil and residual oil raw materials are pretreated through the slurry bed reactors, and then liquid phase materials obtained through gas-liquid separation enter a series of fixed bed reactors to be subjected to demetallization, desulfurization and denitrification advanced refining treatment, so that high-quality hydrogenated oil is obtained.
The disadvantages of this technique or the shortcomings with respect to the present invention: the method is not provided with inferior oil deep hydrocracking equipment, the residual oil conversion depth is insufficient, and the light distillate oil yield is low. And the on-line analysis equipment is not arranged, so that the reaction process of cracking reaction and heavy component condensation coke formation cannot be monitored in time. And no equipment for removing solid particles such as reaction raw coke is arranged, and as the operation time of the device is increased, the bed layer of the fixed bed reactor is blocked by solid particle impurities such as reaction raw coke, so that the pressure drop of the reactor is increased, and the operation period of the device is influenced.
Accordingly, it is desirable to provide a hydrocracking apparatus or process that increases residuum conversion and inhibits reaction coke deposition.
Disclosure of Invention
The invention aims at a slurry bed reactor, an inferior oil slurry bed hydrocracking system and a method, wherein an empty barrel with a spiral channel is arranged in the slurry bed reactor, so that materials in the slurry bed reactor flow in a spiral rising mode, mass transfer is enhanced, and the material flow mode in the slurry bed reactor is optimized; the poor-quality heavy oil slurry bed hydrocracking system and the poor-quality heavy oil slurry bed hydrocracking method can control the coking rate of the poor-quality heavy oil slurry bed hydrocracking reaction to be less than 1 percent (namely, the mass content of toluene insoluble matters in slurry bed hydrocracking generated oil to be less than 1 percent); the quality of the produced gasoline and diesel oil fraction meets the standard requirements of fuel oil for six vehicles in China, and the wax oil fraction meets the quality requirements of feeding or blending feeding of a hydrocracking device; the fraction is completely converted at 500 ℃, no tailings are generated, and the poor-quality heavy oil slurry bed hydrocracking device is kept safe and stable to operate, so that the operating period of the device is effectively prolonged (continuous stable operation is more than 3 years and annual start-up time is more than 8400 hours).
To achieve the above object, the present invention provides a slurry bed reactor comprising a housing, a reactor outlet, a reactor inlet, and a built-in hollow vessel. The outlet of the reactor is arranged at the top of the shell; the reactor inlet is arranged at the bottom of the shell; the built-in empty barrel is arranged in the shell, and spiral fins are arranged between the built-in empty barrel and the shell.
Preferably, the built-in hollow tub and the housing are connected in a spiral form by a spiral fin to form an integral inner member.
Preferably, the two ends of the shell are also provided with flanges, and when the flanges are opened, the inner member is disassembled.
The outer wall of the built-in empty barrel of the slurry bed reactor and the inner wall of the barrel of the slurry bed reactor are connected in a spiral mode to form an integral inner member, and when the slurry bed reactor is stopped and overhauled, the flanges at the two ends of the slurry bed reactor are opened to draw out the integral inner member, so that impurities such as reaction coke on the slurry bed reactor and the inner member can be conveniently cleaned.
Preferably, the number of the spiral fins is a plurality, and the interval between every two spiral fins is 1-10%, preferably 1-5% of the height of the slurry bed reactor; the thickness of the spiral fin is 1-5 mm, preferably 1-3 mm; the width of the spiral fin (the interval between the built-in empty barrel and the inner wall of the barrel of the slurry bed reactor) is 5-15%, preferably 5-10% of the diameter of the slurry bed reactor.
Preferably, the reaction materials are input from the inlet of the reactor and spirally flow into the slurry bed reactor from bottom to top along the flow channels formed by the spiral fins for reaction; the reaction temperature is 380-400 ℃, the reaction pressure is 14.0-18.0 MPa, and the volume airspeed is 1.0-3.0 h -1 The volume ratio of the hydrogen oil is 500-1000.
Preferably, a plurality of electrically heated salt bath modules are arranged in the built-in empty bucket and used for providing auxiliary heating for the slurry bed reactor, and the internal temperature of the slurry bed reactor can be increased by 50-150 ℃.
Preferably, a plurality of temperature pullers which are symmetrically distributed are arranged on the outer wall of the built-in empty barrel and are used for monitoring the temperature in the slurry bed reactor, and two temperature pullers are preferred.
The invention also provides a poor-quality oil slurry bed hydrocracking system, which comprises: the device comprises a first hydrogen mixer, a slurry bed reactor, an online analysis device, a high-pressure separator, a slurry reaction kettle, a fixed bed refining reactor and a fractionation device. The first hydrogen mixer is used for mixing the poor-quality oil raw material containing the catalyst with hydrogen; the first hydrogen mixer is connected with the bottom of the slurry bed reactor, and the mixed poor-quality oil raw material containing the catalyst and hydrogen undergo a preliminary hydrocracking reaction in the slurry bed reactor; the online analysis device is connected with the top of the first hydrogen mixer and the slurry bed reactor and is used for analyzing the product property of the slurry bed reactor and detecting whether the product is qualified or not; the high-pressure separator is connected with the online analysis device and is used for separating qualified products to obtain liquid-phase products and gas-phase products; the slurry reactor is connected with the high-pressure separator and is used for carrying out deep hydrocracking reaction on the inferior oil on the liquid phase product; the fixed bed refining reactor is connected with the slurry reactor and is used for carrying out refining reaction on the product of the slurry reactor; the fractionating device is connected with the first hydrogen mixer and the fixed bed refining reactor and is used for separating the products of the fixed bed refining reactor to obtain high-quality gasoline, diesel oil, wax oil products and hydrogenation tail slag fractions, wherein the hydrogenation tail slag fractions return to the first hydrogen mixer, are mixed with fresh raw materials and then are subjected to preliminary hydrocracking reaction in the slurry bed reactor.
Preferably, the device further comprises a heating furnace, wherein the heating furnace is arranged between the first hydrogen mixer and the slurry bed reactor and is used for heating the mixed poor-quality oil raw material containing the catalyst and the hydrogen.
Preferably, the hydrogen mixer further comprises a second hydrogen mixer, wherein the second hydrogen mixer is arranged between the high-pressure separator and the slurry reaction kettle and is used for mixing liquid-phase products with hydrogen.
Preferably, the reactor also comprises a filter group, a gas-liquid separator and a third hydrogen mixer, wherein the filter group, the gas-liquid separator and the third hydrogen mixer are sequentially arranged between the slurry reactor and the fixed bed refining reactor; the filter group is used for removing large-particle impurities of the reaction coke with the particle size of more than 50 mu m; the gas-liquid separator is used for separating the gas and liquid of the product after removing impurities to obtain a gas-phase material and a liquid-phase material; the third hydrogen mixer is used for mixing the liquid-phase material with hydrogen.
Preferably, the number of slurry reaction kettles is plural, preferably 4-6; the quantity of the slurry reaction kettles meets the continuous operation requirement of processing the pretreatment reaction products of the inferior oil slurry bed reactor and providing raw materials for the fixed bed refining reactor, and the operation conditions are as follows: the reaction temperature is 400-430 ℃, the reaction pressure is 18.0-22.0 MPa, the reaction time is 0.5-2h, and the stirring speed is 10-60r/min.
Preferably, the height-to-diameter ratio of the slurry reaction kettle is 2-15:1, and the height-to-diameter ratio is 5-10:1; the inside of the slurry reaction kettle is provided with stirring equipment, and the upper part of the slurry reaction kettle is provided with a hydrogen injection port for adjusting the reaction pressure and discharging all reaction products after the reaction is finished.
Preferably, the number of fixed bed refining reactors is a plurality, preferably 2; each fixed bed polishing reactor comprises more than two catalyst beds, preferably three catalyst beds, and the operating conditions are as follows: the reaction temperature is 300-380 ℃,the reaction pressure is 5.0-10.0 MPa, and the volume space velocity is 1.5-2.5 h -1 The volume ratio of the hydrogen oil is 300-500:1.
Preferably, the fixed bed refining reactor is used by periodically switching operation, and the fixed bed refining reactor of the poor-quality oil slurry hydrocracking system is used for performing the burning regeneration and activation operation.
Preferably, the on-line analysis device comprises an on-line densimeter, a toluene insoluble matter rapid analyzer, a signal transmission and control computer, and reaction process parameters are timely adjusted by controlling the density and the coke formation of the reaction products.
Preferably, the fractionation device comprises a fractionation furnace, an atmospheric tower, a vacuum tower and a fractionation tower, wherein the fractionation furnace is connected with the fixed bed refining reactor, and the fractionation tower is connected with the first hydrogen mixer, preferably one atmospheric tower is connected with one vacuum tower in series.
Preferably, the catalyst comprises a carrier oil, which is at least one of catalytic diesel, coker diesel, hydrocracker diesel and coker wax oil rich in aromatic hydrocarbons, naphthenes.
Preferably, the poor oil feedstock is at least one of catalytic slurry oil, high sulfur nitrogen residuum, high metal residuum, high carbon residuum, atmospheric residuum, vacuum residuum, super heavy crude oil, and oil sand bitumen.
The invention also provides a hydrocracking method of the poor-quality oil slurry bed, which comprises the following steps:
s1: the inferior oil raw material containing the catalyst is subjected to heat exchange, is mixed with hydrogen in a first hydrogen mixer, is heated by a heating furnace, and enters a slurry bed reactor for preliminary hydrocracking reaction;
s2: detecting whether the reaction product from the step S1 is qualified or not by an online analysis device; if the product is qualified, the product enters a high-pressure separator for separation to obtain a liquid-phase product and a gas-phase product; if the mixture is not qualified, returning to the first hydrogen mixer, mixing the mixture with fresh raw materials, and then carrying out preliminary hydrocracking reaction in the slurry bed reactor again;
s3: the liquid phase product from the step S2 and hydrogen enter a second hydrogen mixer, are mixed in the second hydrogen mixer and enter a slurry reaction kettle for deep hydrocracking reaction of inferior oil;
S4: removing large-particle impurities of the reaction coke with the particle size larger than 50 mu m from the reaction product obtained in the step S3 through a filter group, then, entering a liquid phase material obtained by separation in a gas-liquid separator, mixing the liquid phase material with circulating hydrogen in a third hydrogen mixer, and then, entering a fixed bed refining reactor for refining treatment reaction for removing impurities such as sulfur, nitrogen, metal, aromatic hydrocarbon and the like;
s5: and (3) heating the reaction product from the step (S4) through a fractionating furnace, and separating the reaction product in a fractionating device to obtain high-quality gasoline, diesel oil, wax oil products and hydrogenation tail slag fractions, wherein the hydrogenation tail slag fractions return to a first hydrogen mixer, are mixed with fresh raw materials, and are subjected to preliminary hydrocracking reaction in a slurry bed reactor again.
The method comprises the steps of mixing inferior oil raw materials of a mixed catalyst with hydrogen in a first hydrogen mixer after heat exchange, heating the mixture to a reaction temperature by a heating furnace, then entering a slurry bed reactor for preliminary hydrocracking reaction, judging the properties of a pre-reaction product by an on-line analysis device, fully recycling the pre-reaction product to the first hydrogen mixer for hydrogen mixing if the properties of the pre-reaction product are unqualified, continuously entering the slurry bed reactor for treatment and properly adjusting reaction process parameters, entering a high-pressure separator for gas-liquid separation if the properties of the product are qualified, returning a high-fraction gas-phase product to a circulating hydrogen compressor by a hydrogen compressor for liquid removal and a buffer tank, mixing the high-fraction liquid-phase product with hydrogen provided by a new hydrogen compressor by a pressure reducing valve in a second hydrogen mixer, and entering a slurry reaction kettle for deep conversion of inferior oil. The reaction product enters a filter group to remove large particles of reaction raw coke, then the liquid phase product obtained by gas-liquid separation of a gas-liquid separator is subjected to hydrogen mixing again by a third hydrogen mixer, then enters a fixed bed refining reactor to carry out refining reaction for removing sulfur, nitrogen, metal, slurry bed reaction raw coke and other impurities, then enters a fractionating tower group to carry out separation after being heated by a fractionating furnace, and high-quality gasoline, diesel oil, wax oil and hydrogenation tailing fractions are obtained, and all the hydrogenation tailing fractions are recycled to the first hydrogen mixer to be mixed with fresh raw materials and then participate in the reaction again.
The first hydrogen mixer, the second hydrogen mixer and the third hydrogen mixer are respectively arranged in front of the slurry bed reactor, the slurry reaction kettle and the fixed bed refining reactor, so that the hydrogen dissolution amount of the poor-quality oil slurry bed hydrocracking system can be increased.
The invention optimizes the combined process of a slurry bed reactor, a slurry reaction kettle and a fixed bed refining reactor, follows the idea of gradual cracking and gradual impurity removal, finally realizes high conversion rate of slag oil and obtains fuel oil and high-quality hydrocracking raw materials which meet the national six standards;
the invention preferably adopts a combination means of a filter group and a fixed bed protective agent bed layer, and is used for removing impurities such as coke, solid particles and the like contained in a reaction product step by step.
The invention has the following advantages:
1. improves the conversion rate of residual oil, and inhibits excessive cracking of light components caused by reaction coke deposition and material back mixing. The slurry bed reactor is internally provided with the built-in empty bucket with the spiral channel, so that materials in the slurry bed reactor flow in a spiral rising mode, mass transfer is enhanced, the material flow mode in the slurry bed reactor is optimized, and the residual oil conversion rate of the slurry bed reactor is 1.05-1.25 times of that of the reactor without an inner member under the same reaction process condition; or the reaction severity of the slurry bed reactor is obviously reduced under the same residue conversion rate (the reaction temperature is lower than that of the reactor without internals by 10-30 ℃ and the reaction pressure is lower than that of the reactor without internals by 2-8 MPa). The risk of gravity deposition of the reaction raw coke is effectively reduced; and simultaneously, the risk of light component transitional cracking caused by material back mixing is also inhibited.
2. The hydrogen dissolution amount of the inferior raw material is improved. The invention is provided with a plurality of hydrogen mixers suitable for inferior heavy oil, improves the hydrogen dispersion and mass transfer effect in inferior raw materials, and can achieve 10-20 times of the hydrogen dissolution amount of a common pipeline direct hydrogen injection or a simple hydrogen mixing tank.
3. The method has good product quality and technical economy. The invention adopts the novel slurry bed reactor, a plurality of hydrogen mixers, a filter group, on-line analysis and other equipment, and optimizes the whole process flow by setting a two-stage reaction system of the slurry bed reactor and the slurry reaction kettle and a combined process of the slurry bed and the fixed bed, thereby realizing the design ideas of step-by-step cracking of inferior oil and step-by-step deep refining treatment of the generated oil. Compared with the prior art that the total conversion rate of residual oil is more than 90 percent and the tailing is discharged by 1 to 10 percent, 100 percent of the residual oil is converted into light distillate oil and 0 percent of the tailing is generated; the gasoline and diesel oil fractions obtained by the method meet the fuel oil standard for six vehicles in China, and the wax oil fraction meets the feeding requirement of a hydrocracking device; the reaction coking rate is less than 1%, the continuous and stable operation of the device is more than 3 years, and the annual start time is more than 8400 hours.
4. The invention relates to a poor-quality oil slurry bed hydrocracking system and a method, which are characterized in that the excessive cracking of light components caused by back mixing is restrained by optimizing the material flow form in a slurry bed reactor, a plurality of hydrogen mixers and an online analysis device are arranged, the combined process flow of a slurry bed reactor, a slurry reaction kettle and a fixed bed refining reactor is adopted, the continuous and stable operation of the device is realized on the premise of ensuring the high conversion rate of the poor-quality oil, and the method can be used for directly producing high-quality vehicle fuel oil and hydrocracking raw materials from the poor-quality heavy oil without discharging tailings, so that the high-efficiency and deep conversion process of the poor-quality heavy oil is realized.
Drawings
FIG. 1 is a schematic cross-sectional view of an embodiment of a slurry bed reactor according to the present invention.
Wherein, the reference numerals:
101. reactor outlet 102, flange plate 103, spiral fin 104, built-in cylindrical empty barrel 105, reactor inlet.
FIG. 2 is a schematic process flow diagram of an embodiment of the present invention of a poor oil slurry bed hydrocracking system.
Wherein, the reference numerals:
1. the catalyst preparation tank, 2, the raw oil preparation tank, 3, a raw material pump, 4, a heat exchanger, 5-1, a first hydrogen mixer, 5-2, a second hydrogen mixer, 5-3, a third hydrogen mixer, 6, a heating furnace, 7, a slurry bed reactor, 8, an on-line analysis device, 9, a high-pressure separator, 10, a pressure reducing valve, 11, a slurry reaction kettle, 12, a filter group, 13, a gas-liquid separator, 14, a fixed bed refining reactor, 15, a fractionating furnace, 16, a fractionating tower, 17, a hydrogen compressor and buffer tank, 18, a circulating hydrogen compressor, 19 and a new hydrogen compressor.
FIG. 3 is a schematic flow chart of a conventional slurry bed hydrocracking process for residuum in the prior art.
Wherein, the reference numerals:
1. the catalyst preparation tank 2, the raw oil preparation tank 3, the raw material pump 4, the heat exchanger 5, the inferior oil 6, the slurry bed reactor 7, the high-pressure separator 8, the pressure reducing valve 9, the low-pressure separator 10, the fractionating furnace 11, the fractionating tower 12, the circulating hydrogen compressor 13, the low-fraction liquid removing and buffer tank 14, the compressor liquid removing and buffer tank.
Detailed Description
The invention is further elucidated below in connection with the accompanying drawings.
Referring to fig. 1, fig. 1 is a schematic cross-sectional view of an embodiment of a slurry bed reactor according to the present invention, which includes a shell, a reactor outlet 101, a reactor inlet 105, and a built-in hollow vessel 104. The reactor outlet 101 is arranged at the top of the shell, the reactor inlet 105 is arranged at the bottom of the shell, the built-in empty barrel 104 is arranged in the shell, and the spiral fins 103 are arranged between the built-in empty barrel 104 and the shell.
The present invention is not particularly limited to the number of the helical fins 103, and may be provided in one or more; when the number of the spiral fins 103 is set to be plural, the number thereof may be, for example, 2 to 8, and the interval between every two spiral fins 103 is 1 to 10%, preferably 1 to 5% of the height of the slurry bed reactor; the thickness of the spiral fin 103 is 1 to 5mm, preferably 1 to 3mm; the width of the spiral fin 103 (the interval between the built-in empty barrel 104 and the inner wall of the barrel of the slurry bed reactor) is 5 to 15%, preferably 5 to 10% of the diameter of the slurry bed reactor.
The reactor reaction materials of the slurry bed reactor are input from a reactor inlet 105 and spirally flow into the slurry bed reactor from bottom to top along a flow channel formed by the spiral fins 103 for reaction; the reaction temperature is 380-400 ℃, the reaction pressure is 14.0-18.0 MPa, and the volume airspeed is 1.0-3.0 h -1 The volume ratio of the hydrogen oil is 500-1000.
The inner hollow barrel 104 and the shell are connected in a spiral form through a spiral fin 103 to form an integral inner member. In operation of the slurry bed reactor, feed enters the spiral channels formed by the spiral fins 103 from the reactor inlet 105 at the bottom of the slurry bed reactor and then exits from the reactor outlet 101 at the top. The spiral fins 103 are arranged between the built-in empty barrel 104 and the shell of the slurry bed reactor, the spiral fins 103 are arranged to form spiral channels with the slurry bed reactor, and raw materials flow from bottom to top in a spiral mode after entering the slurry bed reactor, so that mass transfer is enhanced, and the material flow mode in the slurry bed reactor is optimized.
Preferably, a plurality of electrically heated salt bath modules are arranged in the built-in hollow barrel 104 and are used for providing auxiliary heating for the slurry bed reactor, so that the internal temperature of the slurry bed reactor can be increased by 50-150 ℃.
Preferably, a plurality of symmetrically distributed temperature pullers are arranged on the outer wall of the built-in empty barrel 104 and are used for monitoring the temperature in the slurry bed reactor, and the number of the temperature pullers comprises, but is not limited to, 2-4, preferably 2 temperature pullers.
Preferably, the two ends of the shell are also provided with flanges 102, and when the flanges 102 are opened, the inner member can be detached.
The outer wall of the built-in empty barrel 104 of the slurry bed reactor and the inner wall of the slurry bed reactor shell are connected in a spiral mode by adopting the spiral fins 103 to form an integral inner member, and when the slurry bed reactor is stopped and overhauled, the flanges 102 at the two ends of the slurry bed reactor are opened to draw out the integral inner member, so that impurities such as reaction coke on the slurry bed reactor and the inner member can be conveniently cleaned.
Referring to fig. 2, fig. 2 is a schematic process flow diagram of an embodiment of the hydrocracking method for poor oil slurry bed according to the present invention. The poor-quality oil slurry bed hydrocracking system comprises a catalyst preparation tank 1, a raw oil preparation tank 2, a first hydrogen mixer 5-1, a slurry bed reactor, an on-line analysis device, a high-pressure separator, a slurry reaction kettle, a fixed bed refining reactor and a fractionating device.
Mixing the oil-soluble slurry bed hydrocracking catalyst and the carried oil under the stirring condition of a catalyst preparation tank 1; the inferior oil and the catalyst oil containing carried oil from the catalyst preparation tank 1 are mixed under the stirring condition of the raw material preparation tank 2, pumped into the heat exchanger 4 by the raw material pump 3, and the heat exchanger 4 heats the reaction raw material and then inputs the reaction raw material into the first hydrogen mixer 5-1. The first hydrogen mixer 5-1 is used for mixing the catalyst-containing poor oil feedstock with hydrogen. The present invention is not particularly limited in the kinds of the carrier oil and the inferior oil, the carrier oil may be at least one of catalytic diesel oil, coker diesel oil, hydrocracker diesel oil and coker wax oil rich in aromatic hydrocarbon, naphthene, and the inferior oil raw material may be at least one of catalytic slurry oil, high sulfur nitrogen residue, high metal residue, high carbon residue, atmospheric residue, vacuum residue, ultra-thick crude oil, heavy crude oil and oil sand asphalt.
Preferably, a heating furnace 6 is also connected downstream of the first hydrogen mixer 5-1, and the heating furnace 6 is used for heating the mixed poor-quality oil raw material containing the catalyst and hydrogen.
The bottom of the slurry bed reactor 7 is connected with a heating furnace 6, and the mixed poor-quality oil raw material containing the catalyst and hydrogen undergo a preliminary hydrocracking reaction in the slurry bed reactor 7.
An on-line analysis device 8 is connected with the first hydrogen mixer 5-1 and the top of the slurry bed reactor 7, and the on-line analysis device 8 is used for analyzing the product properties of the slurry bed reactor 7 and detecting whether the product is qualified or not. If the product is qualified, the product enters a high-pressure separator 9 for separation to obtain a liquid-phase product and a gas-phase product; if the mixture is not qualified, the mixture returns to the first hydrogen mixer 5-1, is mixed with fresh raw materials, and is subjected to primary hydrocracking reaction in the slurry bed reactor 7 again.
Preferably, the on-line analysis device comprises an on-line densimeter, a toluene insoluble matter rapid analyzer, a signal transmission and control computer, and reaction process parameters are timely adjusted by controlling the density and the coke formation of the reaction products.
The gas phase product is returned to the first hydrogen mixer 5-1 through the recycle hydrogen compressor 18 via the hydrogen compressor deliquified and buffer tank 17.
Preferably, a second hydrogen mixer 5-2 is further included, and the second hydrogen mixer 5-2 is provided between the high-pressure separator 9 and the slurry reactor 11 for mixing the liquid-phase product with hydrogen.
The liquid phase product is mixed with hydrogen provided by a new hydrogen compressor 19 in a second hydrogen mixer 5-2 through a pressure reducing valve 10 and then enters a slurry reaction kettle 11 for deep hydrocracking reaction of inferior oil. The present invention is not particularly limited to the number of the slurry reaction kettles 11, and preferably the number of the slurry reaction kettles 11 is plural, preferably 4 to 6; the number of slurry reaction kettles 11 meets the continuous operation requirement of processing the pretreated reaction product of the poor-quality oil slurry bed reactor 7 and providing raw materials for the fixed bed refining reactor 14, and the operation conditions are as follows: the reaction temperature is 400-430 ℃, the reaction pressure is 18.0-22.0 MPa, the reaction time is 0.5-2h, and the stirring speed is 10-60r/min.
Preferably, the height-to-diameter ratio of the slurry reaction kettle 11 is 2-15:1, and the height-to-diameter ratio is 5-10:1; the inside of the slurry reaction kettle 11 is provided with stirring equipment, and the upper part of the slurry reaction kettle 11 is provided with a hydrogen injection port for adjusting the reaction pressure and completely discharging the reaction products after the reaction is finished.
Preferably, the reactor also comprises a filter group 12, a gas-liquid separator 13 and a third hydrogen mixer 5-3, wherein the filter group 12, the gas-liquid separator 13 and the third hydrogen mixer 5-3 are sequentially arranged between the slurry reactor and the fixed bed refining reactor 14; the filter group 12 is used for removing large-particle impurities of the reaction coke with the particle size of more than 50 mu m; the gas-liquid separator 13 is used for separating gas and liquid of the product after removing impurities to obtain gas-phase materials and liquid-phase materials; the third hydrogen mixer 5-3 is used for mixing the liquid phase material with hydrogen.
The reaction product is subjected to removal of large reaction coke particles larger than 50 mu m through a filter group 12, then enters a gas-liquid separator 13 for gas-liquid separation to obtain a liquid-phase product, and enters a fixed bed refining reactor 14 for refining treatment reaction for removing sulfur, nitrogen, metal, aromatic hydrocarbon and other impurities after hydrogen is mixed again through a third hydrogen mixer 5-3.
The present invention is not particularly limited to the number of fixed-bed refining reactors 14, and the fixed-bed refining reactors 14 may be provided in plural, preferably 2; each fixed bed polishing reactor 14 comprises more than two, preferably three, catalyst beds operated at the following conditions: the reaction temperature is 300-380 ℃, the reaction pressure is 5.0-10.0 MPa, and the volume airspeed is 1.5-2.5 h -1 Hydrogen to oil volume ratio300-500:1. The fixed bed refining reactor 14 is periodically switched for use, and the fixed bed refining reactor 14 of the poor oil slurry hydrocracking system is cut out to perform the burning regeneration and activation operation.
The fractionating device comprises a fractionating furnace 15, an atmospheric tower, a vacuum tower and a fractionating tower 16; the fractionating furnace 15 is connected with the fixed bed refining reactor 14 and is used for heating the product of the fixed bed refining reactor 14, the fractionating tower 16 is connected with the first hydrogen mixer 5-1, the fractionating tower 16 separates the product of the fixed bed refining reactor 14 to obtain high-quality gasoline, diesel oil and wax oil products and hydrogenation tailings fractions, wherein the hydrogenation tailings fractions return to the first hydrogen mixer 5-1, are mixed with fresh raw materials and then are subjected to preliminary hydrocracking reaction in the slurry bed reactor 7. Preferably, an atmospheric tower is used in series with a vacuum tower.
The invention also provides a hydrocracking process for the poor-quality oil slurry bed, which comprises the following steps:
s1: the inferior oil raw material containing the catalyst is subjected to heat exchange, is mixed with hydrogen in a first hydrogen mixer, is heated by a heating furnace, and enters a slurry bed reactor for preliminary hydrocracking reaction;
s2: detecting whether the reaction product from the step S1 is qualified or not by an online analysis device; if the product is qualified, the product enters a high-pressure separator for separation to obtain a liquid-phase product and a gas-phase product; if the mixture is not qualified, returning to the first hydrogen mixer, mixing the mixture with fresh raw materials, and then carrying out preliminary hydrocracking reaction in the slurry bed reactor again;
s3: the liquid phase product from the step S2 and hydrogen enter a second hydrogen mixer, are mixed in the second hydrogen mixer and enter a slurry reaction kettle for deep hydrocracking reaction of inferior oil;
s4: removing large-particle impurities of the reaction coke with the particle size larger than 50 mu m from the reaction product obtained in the step S3 through a filter group, then, entering a liquid phase material obtained by separation in a gas-liquid separator, mixing the liquid phase material with circulating hydrogen in a third hydrogen mixer, and then, entering a fixed bed refining reactor for refining treatment reaction for removing impurities such as sulfur, nitrogen, metal, aromatic hydrocarbon and the like;
S5: and (3) heating the reaction product from the step (S4) through a fractionating furnace, and separating the reaction product in a fractionating device to obtain high-quality gasoline, diesel oil, wax oil products and hydrogenation tail slag fractions, wherein the hydrogenation tail slag fractions return to a first hydrogen mixer, are mixed with fresh raw materials, and are subjected to preliminary hydrocracking reaction in a slurry bed reactor again.
The first hydrogen mixer, the second hydrogen mixer and the third hydrogen mixer are respectively arranged in front of the slurry bed reactor, the slurry reaction kettle and the fixed bed refining reactor, so that the hydrogen dissolution amount of the poor-quality oil slurry bed hydrocracking system can be increased.
The invention optimizes the combined process of a slurry bed reactor, a slurry reaction kettle and a fixed bed refining reactor, follows the idea of gradual cracking and gradual impurity removal, finally realizes high conversion rate of slag oil and obtains fuel oil and high-quality hydrocracking raw materials which meet the national six standards;
the invention preferably adopts a combination means of a filter group and a fixed bed protective agent bed layer, and is used for removing impurities such as coke, solid particles and the like contained in a reaction product step by step.
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Raw material or equipment source:
the raw materials and equipment information are shown in the following table.
Evaluation analysis method:
the evaluation and analysis methods are shown in the following table.
Example 1
The design parameters of the slurry bed reactor used in this example were: the height H of the shell (the distance between the upper flange plate and the lower flange plate) is 2000mm, the diameter R of the shell is 200mm, 6 groups of spiral fins are selected, the distance between the two spiral fins is 1%H (namely 20 mm), the width of each spiral fin is 5% R (namely 10 mm), and the thickness of each spiral fin is 1mm; the inside of the built-in empty bucket is provided with 1 electrically heated salt bath module which is used for providing auxiliary heating for the slurry bed reactor, improving the internal temperature of the slurry bed reactor by 50 ℃, and the outer wall of the built-in empty bucket is provided with 2 symmetrically distributed temperature pullers which are used for monitoring the temperature in the slurry bed reactor.
After the reaction raw materials are mixed with hydrogen in a first hydrogen mixer, the mixture is input from a reactor inlet of a slurry bed reactor and spirally flows from bottom to top along a material flow channel formed by spiral fins to enter the slurry bed reactor for preliminary hydrocracking reaction; the reaction temperature is 380 ℃, the reaction pressure is 14.0MPa, and the volume space velocity is 1.0h -1 Hydrogen oil volume ratio 500. And (3) after the reaction product is analyzed and detected to be qualified by an online analysis device, the reaction product enters a high-pressure separator to separate the product to obtain a liquid-phase product and a gas-phase product.
Mixing the liquid phase product with hydrogen of a second hydrogen mixer, and then carrying out deep hydrocracking reaction on inferior oil in a slurry reactor; in the embodiment, 4 slurry reaction kettles are used, the height-diameter ratio is 5:1, the reaction temperature is 400 ℃, the reaction pressure is 18.0MPa, and the reaction time is 2.0h.
Mixing the product of the slurry reactor with hydrogen of a third hydrogen mixer, and then inputting the mixture into a fixed bed refining reactor for refining reaction; in this example, 2 fixed bed refining reactors were used, each fixed bed refining reactor comprising three catalyst beds, the reaction temperature being 300℃and the reaction pressure being 5MPa, and the volume space velocity being 1.5h -1 Hydrogen oil volume ratio 300. The reaction product is input into a fractionating tower for separation, so that a high-quality product is obtained, the rest of hydrogenation tailings fraction is returned to the first hydrogen mixer, and is mixed with fresh raw materials and then is subjected to preliminary hydrocracking reaction in a slurry bed reactor.
In the embodiment, a slurry reactor is connected with 4 slurry reaction kettles in parallel, and the rear part of the slurry reaction kettle is connected with 2 fixed bed refining reactors in parallel, and the adopted process conditions are shown in Table 2.
Example 2
The design parameters of the slurry bed reactor used in this example were: the height H of the shell (the distance between the upper flange plate and the lower flange plate) is 2000mm, the diameter R of the shell is 200mm, 4 groups of spiral fins are selected, the distance between the two spiral fins is 2.5% H (namely 50 mm), the width of each spiral fin is 7.5% R (namely 15 mm), and the thickness of each spiral fin is 2mm; the inside of the built-in empty bucket is provided with 2 electrically heated salt bath modules which are used for providing auxiliary heating for the slurry bed reactor, improving the internal temperature of the slurry bed reactor by 100 ℃, and the outer wall of the built-in empty bucket is provided with 4 symmetrically distributed temperature pulling devices which are used for monitoring the temperature in the slurry bed reactor.
After the reaction raw materials are mixed with hydrogen in a first hydrogen mixer, the mixture is input from a reactor inlet of a slurry bed reactor and spirally flows from bottom to top along a material flow channel formed by spiral fins to enter the slurry bed reactor for preliminary hydrocracking reaction; the reaction temperature is 390 ℃, the reaction pressure is 16.0MPa, and the volume space velocity is 2.0h -1 Hydrogen oil volume ratio 800. And (3) after the reaction product is analyzed and detected to be qualified by an online analysis device, the reaction product enters a high-pressure separator to separate the product to obtain a liquid-phase product and a gas-phase product.
Mixing the liquid phase product with hydrogen of a second hydrogen mixer, and then carrying out deep hydrocracking reaction on inferior oil in a slurry reactor; in the embodiment, 5 slurry reaction kettles are used, the height-diameter ratio is 7.5:1, the reaction temperature is 415 ℃, the reaction pressure is 20.0MPa, and the reaction time is 1.0h.
Mixing the product of the slurry reactor with hydrogen of a third hydrogen mixer, and then inputting the mixture into a fixed bed refining reactor for refining reaction; in this example, 2 fixed bed refining reactors were used, each fixed bed refining reactor comprising three catalyst beds, the reaction temperature was 340℃and the reaction pressure was 7MPa, and the volume space velocity was 2.0h -1 Hydrogen oil volume ratio 350. The reaction product is input into a fractionating tower for separation, so that a high-quality product is obtained, the rest of hydrogenation tailings fraction is returned to the first hydrogen mixer, and is mixed with fresh raw materials and then is subjected to preliminary hydrocracking reaction in a slurry bed reactor.
In the embodiment, a slurry reactor is connected with 5 slurry reaction kettles in parallel, and the rear part of the slurry reaction kettle is connected with 2 fixed bed refining reactors in parallel, and the adopted process conditions are shown in Table 2.
Example 3
The design parameters of the slurry bed reactor used in this example were: the height H of the shell (the distance between the upper flange plate and the lower flange plate) is 2000mm, the diameter R of the shell is 200mm, 2 groups of spiral fins are selected, the distance between the two spiral fins is 5%H (namely 100 mm), the width of each spiral fin is 10% R (namely 20 mm), and the thickness of each spiral fin is 3mm; the inside of the built-in empty bucket is provided with 3 electrically heated salt bath modules which are used for providing auxiliary heating for the slurry bed reactor, improving the internal temperature of the slurry bed reactor by 150 ℃, and the outer wall of the built-in empty bucket is provided with 6 symmetrically distributed temperature pulling devices which are used for monitoring the temperature in the slurry bed reactor.
After the reaction raw materials are mixed with hydrogen in a first hydrogen mixer, the mixture is input from a reactor inlet of a slurry bed reactor and spirally flows from bottom to top along a material flow channel formed by spiral fins to enter the slurry bed reactor for preliminary hydrocracking reaction; the reaction temperature is 400 ℃, the reaction pressure is 18.0MPa, and the volume space velocity is 3.0h -1 Hydrogen oil volume ratio 1000. And (3) after the reaction product is analyzed and detected to be qualified by an online analysis device, the reaction product enters a high-pressure separator to separate the product to obtain a liquid-phase product and a gas-phase product.
Mixing the liquid phase product with hydrogen of a second hydrogen mixer, and then carrying out deep hydrocracking reaction on inferior oil in a slurry reactor; in the embodiment, 6 slurry reaction kettles are used, the height-diameter ratio is 10:1, the reaction temperature is 430 ℃, the reaction pressure is 22.0MPa, and the reaction time is 0.5h.
Mixing the product of the slurry reactor with hydrogen of a third hydrogen mixer, and then inputting the mixture into a fixed bed refining reactor for refining reaction; in this example, 4 fixed bed refining reactors were used, each fixed bed refining reactor comprising three catalyst beds, the reaction temperature being 380℃and the reaction pressure being 10MPa, and the volume space velocity being 2.5h -1 Hydrogen oil volume ratio 500. The reaction product is input into a fractionating tower for separation, and the product is obtainedAnd (3) returning the rest of hydrogenation tailings fraction to the first hydrogen mixer to obtain a high-quality product, mixing the rest of hydrogenation tailings fraction with fresh raw materials, and then carrying out primary hydrocracking reaction in the slurry bed reactor again.
In the embodiment, a slurry reactor is connected with 6 slurry reaction kettles in parallel, and the rear part of the slurry reaction kettle is connected with 4 fixed bed refining reactors in parallel, and the adopted process conditions are shown in Table 2.
Example 4
The design parameters of the slurry bed reactor used in this example were: the height H of the shell (the distance between the upper flange plate and the lower flange plate) is 2000mm, the diameter R of the shell is 200mm, 6 groups of spiral fins are selected, the distance between the two spiral fins is 1%H (namely 20 mm), the width of each spiral fin is 5% R (namely 10 mm), and the thickness of each spiral fin is 1mm; the inside of the built-in empty bucket is provided with 1 electrically heated salt bath module which is used for providing auxiliary heating for the slurry bed reactor, improving the internal temperature of the slurry bed reactor by 50 ℃, and the outer wall of the built-in empty bucket is provided with 2 symmetrically distributed temperature pullers which are used for monitoring the temperature in the slurry bed reactor.
After the reaction raw materials are mixed with hydrogen in a first hydrogen mixer, the mixture is input from a reactor inlet of a slurry bed reactor and spirally flows from bottom to top along a material flow channel formed by spiral fins to enter the slurry bed reactor for preliminary hydrocracking reaction; the reaction temperature is 380 ℃, the reaction pressure is 14.0MPa, and the volume space velocity is 1.0h -1 Hydrogen oil volume ratio 500. And (3) after the reaction product is analyzed and detected to be qualified by an online analysis device, the reaction product enters a high-pressure separator to separate the product to obtain a liquid-phase product and a gas-phase product.
Mixing the liquid phase product with hydrogen of a second hydrogen mixer, and then carrying out deep hydrocracking reaction on inferior oil in a slurry reactor; in the embodiment, 2 slurry reaction kettles are used, the height-diameter ratio is 5:1, the reaction temperature is 400 ℃, the reaction pressure is 18.0MPa, and the reaction time is 2.0h.
Mixing the product of the slurry reactor with hydrogen of a third hydrogen mixer, and then inputting the mixture into a fixed bed refining reactor for refining reaction; this example used 1 fixed bed finishing reactor, which contains three catalyst beds,the reaction temperature is 300 ℃, the reaction pressure is 5MPa, and the volume space velocity is 1.5 h -1 Hydrogen oil volume ratio 300. The reaction product is input into a fractionating tower for separation, so that a high-quality product is obtained, the rest of hydrogenation tailings fraction is returned to the first hydrogen mixer, and is mixed with fresh raw materials and then is subjected to preliminary hydrocracking reaction in a slurry bed reactor.
In the embodiment, a slurry reactor is connected with 2 slurry reaction kettles in parallel, and the technological process of connecting 1 fixed bed refining reactor behind the slurry reaction kettles is adopted, and the adopted technological conditions are shown in Table 2.
Comparative example 1
Comparative example 1 is a conventional slurry bed hydrocracking process using an operation scheme of a slurry bed reactor without internals, and no slurry reactor and fixed bed refining reactor were provided, and the process flow thereof can be seen in FIG. 3 at high temperature (445 ℃), high pressure (20 MPa), low space velocity (0.8 h -1 ) And (3) under the process condition of high hydrogen-oil ratio (1200:1), carrying out hydrocracking reaction, carrying out gas-liquid separation on the reaction product by high fraction and low fraction, heating the reaction product in a fractionating furnace, and obtaining each fraction product by the fractionating tower.
Comparative example 2
Comparative 2 is a conventional slurry bed hydrocracking process employing two slurry bed reactors without internals, one section of series operating scheme, at a reaction temperature of 430 ℃, a reaction pressure of 18MPa, a low space velocity (1.0 h) -1 ) High hydrogen-oil ratio>800:1), the first reaction product directly enters the second reaction without separation, the second reaction product is subjected to gas-liquid separation by high-fraction and low-fraction, enters a fractionating furnace for heating, and then enters a fractionating tower for obtaining each fraction product.
Comparative example 3
This comparative example differs from example 4 only in that: this comparative example uses the same operating scheme as in example 4 with other apparatus and reaction parameters for a spiral fin free slurry bed reactor.
The slurry bed hydrocracking catalyst used in the invention is an oil-soluble high-dispersion molybdenum-based catalyst, and can be directly used after being heated to an activation temperature without presulfiding during use. The properties of the raw materials used in the examples and comparative examples are shown in Table 1.
TABLE 1 oil Properties of raw materials
The process conditions used in the examples and comparative examples are detailed in Table 2.
Table 2 operating conditions of examples and comparative examples
The test results of the examples and comparative examples are shown in Table 3.
TABLE 3 test results
As is clear from tables 1 to 3, the heavy oil conversion rate of comparative example 1 using one internalless slurry bed reactor of the conventional slurry bed hydrocracking process was 91.4%, the coking rate was 7.5%, the heavy oil conversion rate of comparative example 2 using two internalless slurry bed reactors of the conventional slurry bed hydrocracking process was 92.1%, the coking rate was 4.6%, the heavy oil conversion rate of comparative example 3 using a spiral-fin-free slurry bed reactor was 92.8%, the coking rate was 2.3%, and the heavy oil conversion rate of example 1 employing the present invention (slurry bed reactor+slurry reactor+fixed bed reactor with empty drum internals having spiral fins) was 94.3%, the coking rate was only 0.12%; the heavy oil conversion of example 2 was 97.0% and the coking rate was only 0.3%; the heavy oil conversion of example 3 was 100% and the coking rate was 0.91%; the heavy oil conversion of example 4 was 94.1% and the coking rate was 0.72%.
When the conventional slurry bed process scheme is adopted, the two slurry bed reactors have certain advantages compared with one slurry bed reactor, and the heavy oil conversion rate is slightly increased under the condition that the reaction severity is relatively reduced.
Compared with the conventional slag oil slurry bed hydrocracking process, the method has obvious advantages, and due to the arrangement of the spiral fins, the full-distillate oil has good property, sulfur, nitrogen, metal and other impurities are basically removed completely while the reaction severity is further reduced (the reaction temperature and the reaction pressure are lower), the gasoline and diesel oil fractions obtained after fractionation can meet the national six standards, the light oil yield is higher than 70%, and the continuous running time of the device is longer than 2500 hours.
The invention adopts the optimized process method of a plurality of hydrogen mixers, multi-point hydrogen supplementing, grading reaction and on-line control, designs and adopts the combination scheme of a slurry bed pre-reactor, a slurry reaction kettle and a fixed bed refining reactor, realizes continuous and stable operation of the device on the premise of high conversion rate of inferior oil, can directly produce high-quality vehicle fuel oil or chemical raw materials from the inferior heavy oil, has no tailings discharge, and finally realizes the high-efficiency and deep conversion process of the inferior heavy oil.
The above examples are exemplary examples listed for the purpose of describing the technical solution of the present invention in detail, the present invention is subject to the protection scope of the claims and the summary of the invention, and is not limited by the embodiments, and the simple substitution or modification of the present invention is still within the protection scope of the present invention.
Claims (15)
1. A slurry bed reactor, comprising:
a housing;
the reactor outlet is arranged at the top of the shell;
the reactor inlet is arranged at the bottom of the shell; and
the built-in empty barrel is arranged in the shell, and spiral fins are arranged between the built-in empty barrel and the shell.
2. The slurry bed reactor according to claim 1, wherein the built-in hollow tub and the shell are connected in a spiral form by the spiral fin to form an integral inner member; and flange plates are arranged at two ends of the shell, and the inner member is disassembled when the flange plates are opened.
3. Slurry bed reactor according to claim 1, characterized in that the number of spiral fins is a plurality, the spacing between every two spiral fins being 1-10%, preferably 1-5% of the slurry bed reactor height; the thickness of the spiral fin is 1-5 mm, preferably 1-3 mm; the width of the spiral fin is 5-15%, preferably 5-10% of the diameter of the slurry bed reactor.
4. The slurry bed reactor according to claim 1, wherein a reaction material is fed from the reactor inlet and flows spirally from bottom to top along the flow channels formed by the spiral fins into the slurry bed reactor for reaction; the reaction temperature is 380-400 ℃, the reaction pressure is 14.0-18.0 MPa, and the volume airspeed is 1.0-3.0 h -1 The volume ratio of the hydrogen oil is 500-1000.
5. The slurry bed reactor according to claim 1, wherein a plurality of electrically heated salt bath modules are arranged in the built-in empty bucket and used for providing auxiliary heating for the slurry bed reactor and improving the internal temperature of the slurry bed reactor by 50-150 ℃; the outer wall of the built-in empty barrel is provided with a plurality of temperature pulling instruments which are symmetrically distributed and are used for monitoring the temperature in the slurry bed reactor, and two temperature pulling instruments are preferred.
6. A poor quality oil slurry bed hydrocracking system, comprising:
the first hydrogen mixer is used for mixing the poor-quality oil raw material containing the catalyst with hydrogen;
the slurry bed reactor according to any one of claims 1 to 5, wherein the first hydrogen mixer is connected with the bottom of the slurry bed reactor, and the mixed poor-quality oil raw material containing the catalyst and hydrogen undergo preliminary hydrocracking reaction in the slurry bed reactor;
the online analysis device is connected with the first hydrogen mixer and the top of the slurry bed reactor and is used for analyzing the product property of the slurry bed reactor and detecting whether the product is qualified or not;
the high-pressure separator is connected with the online analysis device and is used for separating qualified products to obtain liquid-phase products and gas-phase products;
the slurry reactor is connected with the high-pressure separator and is used for carrying out deep hydrocracking reaction on the liquid phase product with inferior oil;
the fixed bed refining reactor is connected with the slurry reaction kettle and is used for carrying out refining reaction on the product of the slurry reaction kettle; and
the fractionation device is connected with the first hydrogen mixer and the fixed bed refining reactor and is used for separating products of the fixed bed refining reactor to obtain high-quality gasoline, diesel oil and wax oil products and hydrogenation tail slag fractions, wherein the hydrogenation tail slag fractions return to the first hydrogen mixer and are mixed with fresh raw materials and then are subjected to preliminary hydrocracking reaction in the slurry bed reactor again.
7. The poor oil slurry bed hydrocracking system of claim 6, further comprising a heating furnace disposed between said first hydrogen mixer and said slurry bed reactor for heating said mixed catalyst-containing poor oil feedstock with hydrogen.
8. The poor oil slurry bed hydrocracking system of claim 6, further comprising a second hydrogen mixer disposed between the high pressure separator and the slurry reactor for mixing the liquid phase product with hydrogen.
9. The poor-quality oil slurry bed hydrocracking system according to claim 6, further comprising a filter group, a gas-liquid separator and a third hydrogen mixer, wherein the filter group, the gas-liquid separator and the third hydrogen mixer are sequentially arranged between the slurry reactor and the fixed bed refining reactor; the filter group is used for removing large-particle impurities of the reaction coke with the particle size of more than 50 mu m; the gas-liquid separator is used for separating gas and liquid of the products from which impurities are removed to obtain gas-phase materials and liquid-phase materials; the third hydrogen mixer is used for mixing the liquid-phase material with hydrogen.
10. The poor oil slurry bed hydrocracking system of claim 6, wherein the number of slurry reaction kettles is a plurality, preferably 4-6; the quantity of the slurry reaction kettles meets the continuous operation requirement of processing the pretreatment reaction products of the inferior oil slurry bed reactor and providing raw materials for the fixed bed refining reactor, and the operation conditions are as follows: the reaction temperature is 400-430 ℃, the reaction pressure is 18.0-22.0 MPa, the reaction time is 0.5-2h, and the stirring speed is 10-60r/min; the height-diameter ratio of the slurry reaction kettle is 2-15:1, and the height-diameter ratio is 5-10:1 preferably; the inside of slurry reactor sets up agitated vessel, slurry reactor's upper portion sets up annotates hydrogen mouth for adjust reaction pressure and after the reaction finishes with the whole discharge of reaction product.
11. The poor oil slurry bed hydrocracking system of claim 6, wherein the number of fixed bed refining reactors is a plurality, preferably 2; each fixed bed refining reactor comprises more than two catalyst beds, preferably three catalyst beds, and the operating conditions are as follows: the reaction temperature is 300-380 ℃, the reaction pressure is 5.0-10.0 MPa, and the volume airspeed is 1.5-2.5 h -1 The volume ratio of hydrogen to oil is 300-500:1; the fixed bed refining reactor is switched to operate periodically, and the fixed bed refining reactor for cutting out the poor-quality oil slurry hydrocracking system executes the operations of burning regeneration and activation.
12. The poor-quality oil slurry bed hydrocracking system according to claim 6, wherein the on-line analysis device comprises an on-line densimeter, a toluene insoluble matter rapid analyzer, a signal transmission and control computer, and the reaction process parameters are timely adjusted by controlling the density and the coke formation of the reaction products.
13. The poor quality oil slurry bed hydrocracking system according to claim 6, wherein the fractionation device comprises a fractionation furnace, an atmospheric tower, a vacuum tower, and a fractionation tower, wherein the fractionation furnace is connected with the fixed bed refining reactor, and the fractionation tower is connected with the first hydrogen mixer, preferably one atmospheric tower is connected with one vacuum tower in series.
14. The poor quality oil slurry bed hydrocracking system of claim 6, wherein the catalyst comprises a carrier oil, the carrier oil being at least one of an aromatic, naphthenic enriched catalytic diesel, coker diesel, hydrocracker diesel, and coker wax oil; the inferior oil raw material is at least one of catalytic slurry oil, high sulfur nitrogen residual oil, high metal residual oil, high carbon residual oil, atmospheric residual oil, vacuum residual oil, super thick crude oil, heavy crude oil and oil sand asphalt.
15. A poor quality oil slurry bed hydrocracking method, which is characterized by comprising the following steps:
s1: after heat exchange, the poor-quality oil raw material containing the catalyst is mixed with hydrogen in a first hydrogen mixer, heated by a heating furnace and enters the slurry bed reactor of any one of claims 1-5 for preliminary hydrocracking reaction;
s2: detecting whether the reaction product from the step S1 is qualified or not by an online analysis device; if the product is qualified, the product enters a high-pressure separator for separation to obtain a liquid-phase product and a gas-phase product; if the mixture is not qualified, returning to the first hydrogen mixer, mixing the mixture with fresh raw materials, and then carrying out preliminary hydrocracking reaction in the slurry bed reactor again;
s3: the liquid phase product from the step S2 and hydrogen enter a second hydrogen mixer, are mixed in the second hydrogen mixer and enter a slurry reaction kettle for deep hydrocracking reaction of inferior oil;
s4: removing large-particle impurities of the reaction coke with the particle size larger than 50 mu m from the reaction product obtained in the step S3 through a filter group, then, entering a liquid phase material obtained by separation in a gas-liquid separator, mixing the liquid phase material with circulating hydrogen in a third hydrogen mixer, and then, entering a fixed bed refining reactor for refining treatment reaction for removing impurities such as sulfur, nitrogen, metal, aromatic hydrocarbon and the like;
S5: and (3) heating and separating the reaction product from the step (S4) through a fractionating device to obtain high-quality gasoline, diesel oil, wax oil products and hydrogenation tail slag fractions, wherein the hydrogenation tail slag fractions return to the first hydrogen mixer, are mixed with fresh raw materials, and are subjected to preliminary hydrocracking reaction in a slurry bed reactor again.
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| CN116726807A (en) * | 2023-08-15 | 2023-09-12 | 北京拓川科研设备股份有限公司 | Temperature pulling system applied to fixed bed reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116726807A (en) * | 2023-08-15 | 2023-09-12 | 北京拓川科研设备股份有限公司 | Temperature pulling system applied to fixed bed reactor |
| CN116726807B (en) * | 2023-08-15 | 2023-12-22 | 北京拓川科研设备股份有限公司 | Temperature pulling system applied to fixed bed reactor |
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